Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheimer, New York, N. Y.

No Drawing. Application March 6, 1956, Serial No. 569,693

6 Claims. (Cl. 260-458) This invention relates to novel compositions and to methods for making them. in one of its more specific aspects, the invention is directed to methods of making and to novel derivates of a certain class of starting materials. Said starting materials are amino carboxylic acid metal salts, which I shall hereinafter refer to as amino acid metal salts.

Said amino acid metal salts are useful as surface active agents, are employed as starting materials in the practice of this invention, and have the following general Formula I:

in which R is a hydrocarbon radical of at least 6 carbon atoms and preferably 6-18 carbon atoms, and for most purposes R is preferably such a radical which may be either aliphatic and straight or branch chain or cycloaliphatic or aliphatic-aromatic, with the aliphatic portion being attached to an aromatic nucleus and having at least 3 carbon atoms; Y is selected from the class consisting of Rs and R2-COOM; R2 is an organic group selected from the class consisting of (a) aliphatic, aromatic or aromatic-aliphatic hydrocarbon groups of 1-12 carbon atoms, such as -CH2, -C2H4, C3Hc, C4Hs-, C5H10, COH, CeH4, -CsI-I4CH2-, (b)'hydroxy substituted aliphatic hydrocarbon groups of 1-12 carbon atoms, illustrative examples of which are (c) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, illustrative examples of which are (d) aliphatic ether groups, each of said group having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, illustrative example of which is (e) aliphatic keto groups, each of said groups having a single carbonly linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, illustrative example of which CH2COCH2, (f) aliphatic keto groups, each of said groups having a single carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, illustrative example of which is (g) aliphatic keto-ether groups, eachof said groups -having ether oxygen and single carbonyl linkages therein and otherwise being hydrocarbon or hydroxy substituted hydrocarbon of 2-12 carbon atoms; R0 is selected from the class consisting of hydrogen and monovalent radicals otherwise defined in (a)(g), examples of which are -cHeCOCHs These various amino acid metal salts may be prepared in a number of different ways well known to the art, among which are the following: 1 mol of C9H19CsH4-NH2 is reacted with l and 2 mols respectively of an appropriate monohalomonocarboxylic acid, such as monochloracetic in the presence of aqueous caustic soda, to provide compounds hereinafter known as products A and B respectively, and having the following formulas:

/H CQHIQ N CH -CO ONa and CHr-CO ONa CnHm- CHI-00 ON'a respectively; 1 mol of CQHlQ-NH2 may first be reacted with 1 mol of methyl chloride and ethylene chlorhydrin respectively, and subsequently reacted with 1 mol of chloracetic acid in the presence of aqueous caustic soda to provide compounds hereinafter known as products C and D, having the following formulas:

CH; CQHlPN C Hr-C O O Na and C2 4O H cpHn -N CHz-C O 0 Na respectively; 1 mol of CsH13NH2 may be reacted with 1 mol of monochlorlactic acid in the presence of aqueous caustic soda to provide compound hereinafter known as product E, having the following formula:

CuHu-N CHQCHOH-COONd 1 mol of C1aH35--NH2 may be reacted with 1 and 2 mols of monochlorethoxyacetic acid in the presence of aqueous caustic soda and potassium hydroxide respectively, to provide compounds hereinafter known as products F and G respectively, having the following formluas:

H C1s ar ce lO CHI-C 0 OK and CIHAO CHr-C 0 OK Clams- CHrCO CHQOH GHQ-000M;

respectively; 1 mol of CaH17'NH2 is reacted with 1 mol of ethylene chlorhydrin and subsequently reacted with 1 mol of monochlorethoxy acetic acid in the presence of aqueous potassium hydroxide, to provide compound hereinafter known as product K and of the following formula:

and

CsHn- CzH|OCHaCOOK 1 mol of CsH1sNH2 is reacted with glycerine chlorhydrin, and dimethyl dihydroxyketone chlorhydrin respectively and 1 mol of each of the resulting compounds are reacted with 2 mols of monochloracetic acid in the presence of caustic soda to provide products L and M of the following formulas:

CHzCHOHCHrO CHr-OOONa CaHn- CHr-GOONa and H CH|C O CHO CHr-C O ONa eHxa-N CHa-CO 0N5 respectively; 1 mol of CrzI-Iss-NHz is reacted with 2 mols of glycerine oxide CHr-CHOHsOH and then with 2 mols of monochloracetic acid in the presence of caustic soda in aqueous solution to provide product N of the following formula:

O'HaOHOHCI-IQO CHs-COONa Cn sr- OHz CHOHCHaOOHn-COONa 1 mol of a polyethoxy amine, such as diethoxy amine is first reacted with 1 mol of C11H23Cl and 1 mol of resulting compound is reacted with 1 mol of rnonochlorpropionic acid in the presence of potassium hydroxide or with acrylonitrile (CH2=CHCN) and subsequently hydrolized to provide product 0 of the following formula:

1 mol C1oH21--NH2 is first reacted with one mol of methyl chloride and subsequently reacted with 1-5 mols of ethylene oxide or 1-4 mols of propylene oxide and, in this specific instance, 3 mols of ethylene oxide and then with 1 mol of monochloracetic acid in the presence of caustic soda to provide product P having the follow ing formula:

iHiononl-co 0N8 CroHn-N 1 mol of 2 4 :E illan-N sHi in which x is 1-5, and in this instance is .4, is reacted with 1 and 2 molsof monochloracetic acid respectively in the presence of caustic soda, to provide products Q and R respectively having the following formulas:

(C3HtO)a csHr-O O ONa O nHza-N aHtO)aH and ( al-I00 02114-0 O ONa CnHas-N (CaHsO)sCzH4-COONa 1 mol of CuHzx-NHa is reacted in the presence of an aqueous solution of 2 mols of caustic soda with 1 mol 7 of the following: ClCsHiCOOI-I and ClCHzCeHaCOOI-I to respectively provide two compounds hereinafter known as productsT-l and T-2 and having the following respective formulas:

omooom 1 mol of product CnHzs-NHz is first reacted with 1 mol of ClCsHs and then with 1 mol of chloracetic acid in the presence of caustic soda to provide a compound having the following formula and known as product T-3:

and

OnHas-N OHzCOONa j 1 mol of product I is reacted with 1 mol of monochloracetic acid in the presence of caustic soda to provide compound hereinafter known as product U having the following formula:

v OHsCOCHzOCHzOOONa CoHn-N GH2COON21 The radical R of all of the formulas hereinbefore and hereinafter set forth is that hereinbefore defined in connection with Formula I. Instead of employing monochloracetic acid, any other appropriate monohalornonocarboxylic acid, such as monochlorpropionic, monochlorlactic acids, etc. may be employed. Thus, by merely substituting the particular monohalomonocarboxylic acid for those used in the production of the particular compounds hereinbefore set forth, and/or by employing the various radicals and groups for R6 and R2 but Within the definitions thereof as heretofore defined, avery great number arouses of products X, examples of which are products A-H and J-U, are amino acid metal salts, which may be employed as starting materials or reactants in the practice of this invention.

Prior to this invention, it was known that cationic surface active agents and anionic surface active agents when together in aqueous solution resulted in the production or formation of water insoluble compounds; and that adding an anionic surface active agent to an aqueous solution of another anionic surface active agent resulted in a mere physical combination of said agents and that no reaction would occur between them.

Said amino acid metal salts normally behave anionically in aqueous solutions having .a pH above 7, and consequently it was expected that said amino acid metal salts when in aqueous solution together with anionic surface agents that they would be combined physically only and that no chemical reaction would occur therebetween. In the course of my experimentations, I have discovered that said amino acid metal salts could be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not only did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of the amino acid metal salts and also exhibited better foaming characteristics than did said amino acid metal salts in very low dilutions under extreme water hardness conditions. Said reaction products are non-toxic and non-irritating to the human skin. They have been found eminently useful as general utility detergents, such as for car washing, dish washing, clothes washing, etc. Said amino acid metal salts when used as component of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and water solutions thereof accidentally reached the eyes. I have further discovered that the reaction products of this invention cause-d practically no irritation or stinging of the eye when so employed.

According to this invention, one or a combination of two or more of said amino acid metal salts of the general structural Formula I are reacted with one or a combination of two or more anionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula III, and having high wetting, detergency, and surface active properties and capable of providing voluminous and stablefoams in aqueous solutions, and which aqueou solutions are substantially nonirritating to the skin and eyes of normal human beings.

FORMULA II Ra-Z-( Cal-L) e-SOs -M FORMULA III wherein R3 is a hydrocarbon radical, generally aliphatic or aliphatic-aromatic, and having at least 6 carbon atoms and for most purposes 6-2O carbon atoms; Z is either oxygen or sulphur; and x is an integer and being at least 1 and generally 1-5, and preferably 3; M, R, Y and R2 have heretofore been defined in Formula I.

According to this invention, I react a compo nd of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general, this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for ex ample hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approx mately 10.0- 200 In this reaction under the aforesaid conditions, the compounds of Formula III are produced, aid compounds having high water solubility in spite of the fact that the number of carbon atoms in Rs is-6 or more. Such compounds of Formula III have an unexpected extremely high water-solubility, while the corresponding salts of cationic compounds' are water-insoluble. The resultant aqueous solution can be used directly as a surface active agent, wetting agent or detergent for the, purposes indicated for the amino acid metal salts. While the quantities of the compound of Formula I and compound of Formula II may be equimolecular for good yield of compounds of Formula III, I may employ an excess of either, and in general the mole ratio of a compound of Formula I to compound of Formula II may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueou caustic soda if required so that when a compound of Formula II is added thereto, the pH of the solution of I and II will be at least 10 and generally 10.5-11. The temperature of said solution is raised to l00-200 F. and preferably in factory practice to approximately P. Then a quantity of a compound of Formula II is dissolved in water in a separate container and this solution is added to said first solution and the mas is maintained in said temperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

Example 1 An aqueous solution of 400 parts of product A in 450 parts of water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 12-13. While being constantly stirred and maintained at that temperature, there is added a solution of 400 parts of sodium salt of lauryldiethoxyether sulfate:

in 600 parts of water. Then while stirring and the temperature is maintained there is added thereto between about 30-40 parts of hydrochloric acid solution (32%) whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 1 0 minutes more. The resultant product is a solution of the novel reaction product having the following formula:

w II

Employ the same procedure and components as set forth in Example 1, except that only about 200 parts of the sodium salt of lauryldiethoxyether sulfate are used. In this instance, the resultant product is a solution of the novel reaction product whose structural formula is shown in Example 1 together with unreacted product A used, in the approximate proportion of two parts of the former to one of the latter.

7 Employ the same procedure as that set forth in Example 1, but employ the components indicated in the following Examples 3-21; the quantity of hydrochloric acid solution (32%) is variable to lower the pH to values indicated in Example 1 to obtain the novel reaction products of said Examples 3-21.

Example 3 380 parts of product B in 600 parts of water. of octylmonoethoxyether sulfate sodium salt:

CsHrz-O(C2HO )SOs-Na in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT GHQ-C 0 Na 0H1s /N\ H CH3 O O ONa CBHHO (OZHLO) S Oz 250 parts Example 4 240 parts of product C in 360 parts of water. 500 parts of tridecyl tetraethoxyether sulfate sodium salt:

C1aH27-O-(C2H4O)4SOaNa in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CoH1sN H GHQ-O 0 ON).

O1:Hz1O(C H4O)r-SO:

Example 5 270 parts of product D in 405 parts of water. 500 parts of nonylphenoltriethoxy ether sulfate sodium salt:

C9H19CsH4O-(C2H4O 3SOa-Na in 750 parts of water.

FORMULA OF NOI'EL REACTION PRODUCT CzHq OH C9HlD N H CHz C O ONa Example 6 210 parts of product E in 315 parts of water. 250 parts of hexylmonoethoxy thioether sulfate sodium salt:

C6H18S-(C2H40)-SO3N3 in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CoHw- H CHaCHOH-OOONa OQHIBS (O:H4O)SO;

Example 7 390 parts of product F in 585 parts of water. 600 parts of stearoylpentaethoxy thioether sulfate sodium salt:

C17H35S( C2H40) 5-SO3Na in 900 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CraHas-N H C2H4O CHr-COOK C11 aa -(C2H4Ois-SOx V Example8 270 parts of product G in 405 parts of water. 350 parts of octylphenol diethoxy thioether sulfate potassium salt:

5 CaH11-CeH4-43(C2H4O 2-SO3K in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT C2H4O CHzC 0 OK ClaH N H CQH4OCH5-COOK CaHuCuH4-S(C2H40)n-S 0: Example 9 350 parts of product H in 500 parts of water. 400 parts of decyltriethoxy thioether sulfate sodium salt:

C1oH21S(C2I-I4O 3SO3Na in 600 parts of water. 7 FORMULA OF NOVEL REACTION PRODUCT OHQCHOHOHaOH GnH1a-C0H4-N 5 CHzC O ONn CroHn-S (CgH)3-S 03 Example 10 320 parts of product I in 480 parts of water. 500 parts 30 of amylphenylpentaethoxy ether sulfate sodium salt:

C5H1 1-C6H4O CzH4O 5SOsNa in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT Example 11 375 parts of product K in 550 parts of water. 280 parts of tridecyltetraethoxy thioether sulfate potassium salt:

C13S27S- C2H4O 4SO3K in 75 0 parts of water.

FORMULA OF NOVEL REACTION PRODUCT mmon aHn-N 11 C:H4O OHI -COOK CnHn-S-(CaI-ROM-S 0a 5 Example 12 400 parts of product L in 600 parts of water. 400 parts of potassium salt of lauryl diethoxyether sulfate sodium salt:

400 parts of product M in 600 parts of water. 250 parts of octyl monoethoxy ether sulfate sodium salt:

CsH1'IO(CaH40)-SO3--Na 5 in, 400 parts of water. I

average FORMULA OI! NOVEL REACTION PRODUCT O Gila-CO T/HO (3111- 0 0N8 CoH1:N

H CH: -O O ONa aHu0-(CzH0)-$Oa Example 14 475 parts of product N in 620 parts of water. 500 parts of tridecyl tetraethoxy ether sulfate sodium salt:

C1aH27O-(C2H4O 4-SO3Na in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CHzCHOHCHzO CHz-C 0 ONa l'lH86 H CHzCHOHOzOCIh-COONa CIIHZI-O(GQH40)4SOI Example 15 350 parts of product 0 in 525 parts of water. 500 parts of nonylphenoltriethoxyether sulfate sodium salt:

C9H19-CsH4-O-(C2H4O)3SOs-Na in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT (C2H4O)2H Cn'Hsr-N H CaIHr-C O O K C0H1r-CoHtO*'-(C5H4O)r-SOs Example 16 350 parts of product P in 525 parts of water. 250 parts of hexyl monoethoxythioether sulfate sodium salt:

C6H13'S-(C2H40)S03-Na in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT (O2H|O)3CH1OOONB Olefin- 500 parts of product Q in 750 parts of water. 600 parts of stearoyl pentaethoxythioether sodium salt:

C17H35S-(C2H4O)5-SOs-N-a in 900 parts of water.

FORMULA OF NOVEL REACTION PRODUCT (C2H40)(CH:COON3 CBHIP N H (C2HO)4H C11Hu- (C:Ht )a 0:

Example 18 680 parts of product R in 1,000 parts of water. 350 parts of octyl phenol diethoxy thioether sulfate sodium t: Sal CaH17CsH4-S- C2H4O 2SO3Na in 500 parts of water.

FORMULA OF NOVEL REACTION PRODUCT aH4O)4CHzCOONa CnHm- H (CaH4O)4CH2-COONa sHi7-CoH|- -(C:HtO)r-SO:

Example 19 590 parts of product S in 890 parts of water. 400 parts of decyltriethoxy thioethersulfate sodium salt:

C10H215-( C2H4O 3SOs-Na in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT (OaHoO)aC1H|-C 0 ON:

CnHzr-N O10Hu-S -(C:H|O) SO:

Example 20 700 parts of product T in 1,050 parts of water. 500 parts of amylphenylpentaethoxy ether sulfate sodium salt:

C5H11C6H4O(C2H40) 5SO3Na in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT (CzHoO)aCaH-C O ONa 1IH2J- H (O:HaO)sC:H4-CO ONa CaHnCoH4O(C:H4O)t-S 0:

Example 21 350 parts of product U in 525 parts of water. 280 parts of tridecyltetraethoxy thioether sulfate potassium salt:

C13H27S(C2H4O 4-SO3-K in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CHIC O CHaO CHr-CO 0N3.

CvHrv H CHr- C O 0N3 C1sH21- i )4-S 0:

Following the same procedure as that set forth in Example 1, and employing 1 mole of any of the other reactants of Formula I and 1 mole of any of the other reactants of Formula II, a great number of other novel reaction products, Whose formulas are those of Formula III, may be produced. It is also to be understood that any of said reactants of Formula I may be specifically diiferent from those shown in the foregoing by substituting any for the particular R shown, a radical such as C12H25, which is preferable, or any other hydrocarbon radical of 6-18 carbon atoms, Y and R2 also may be varied so that a great variety of starting materials may be used.

Also, other reactants of Formula Ii may be employed in the specific examples, the R3, Z, and x may be varied.

It is to be understood that instead of first adjusting the pH of the compound of Formula I to 12-13 before the addition of the compound of Formula II, any other method may be employed to obtain the condition whereby the pH of the solution of I and II is at least 10 and preferably 10.541 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and Il may be dissolved together and this solution may, by the addition of caustic soda when required, have its pH adjusted to at least 10, and then at 200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution of pH of at least 10 is brought to a temperature in the range of 100-200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

I claim:

1. A compound of the following formula:

R--N H/ Rr-COOM R|Z(C:H40)=SO: in which R is a hydrocarbon radical of 6-18 carbon atoms; Y is selected from the class consisting of R6 and Rz-COOM; R2 is an organic group selected from the class consisting of (a) aliphatic, aromatic and aromaticaliphatic hydrocarbon groups of 1-12 carbon atoms, (b) hydroxy substituted aliphatic hydrocarbon groups of 1-12 carbon atoms, (c) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (d) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (e) aliphatic keto groups, each of said groups having a single carbonyl linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (f) aliphatic keto groups, each of said groups having a single carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (g) aliphatic ketoether groups, each of said groups having ether oxygen and single carbonyl linkages therein and otherwise being hydrocarbon of 2-12 carbon atoms, (h) aliphatic ketoether groups, each of said groups having ether oxygen and single carbonyl linkages therein and otherwise being hydrocarbon of 2-12 carbon atoms; R6 is selected from the class consisting of (1') hydrogen and (j) monovalent radicals otherwise defined in (a)-(h); R3 is a radical selected from the class consisting of (k) aliphatic and aliphatic-aromatic hydrocarbon radicals of 6-20 carbon atoms; Z is selected from the class consisting of oxygen and sulphur; x is 1-5; and M is an alkali metal.

2. A compound of the following formula:

in which R is aliphatic hydrocarbon of 6-18 carbon atoms and lie is aliphatic hydrocarbon of 6-20 carbon atoms; x s 4. A compound of the following formula:

' CHz-COON R-N H/J \CH1CO ONa Rs-O(C2H40); 0a

in which R is aliphatic hydrocarbon of 6-18 carbon atoms; iRalis5 aliphatic hydrocarbon of 6-20 carbon atoms; and x S 5. compound of the following formula:

' omooomo om-oooNa R-N 11 CHa-COONa s (C2H4Q)=SOz in which R is aliphatic hydrocarbon of 6-18 carbon atoms; gslissali-phatic hydrocarbon of 6-20 carbon atoms; and x 6. A compound of the following formula:

CraH:aN

H OHr-G 0 0 Na C1:H2sO(CzH 0)sSO:

References Cited in the file of this patent UNITED STATES PATENTS 2,097,640 Piggott Nov. 2, 1937 FOREIGN PATENTS 208,288 Switzerland Apr. 16, 1940 

1. A COMPOUND OF THE FOLLOWING FORMULA: 